JP6788372B2 - Alkaline developable resin composition, dry film, cured product and printed wiring board - Google Patents

Description

The present invention relates to alkali-developable resin compositions, dry films, cured products and printed wiring boards.

In recent years, in response to the increasing density of printed wiring boards due to the miniaturization of electronic devices, BGA has replaced IC packages called QFP (quad flat pack package), SOP (small outline package), etc. Semiconductor packages called (ball grid array), CSP (chip scale package), etc. have appeared. In a printed wiring board having a fine pitch wiring pattern such as a semiconductor package, the wiring patterns are formed at high density and close to each other, so that short circuits and crosstalk noise occur between the lines of the wiring pattern. Since it is likely to occur, a particularly high degree of reliability is required for a permanent coating on a printed wiring board such as a solder resist.

However, the alkali-developed resin composition used as a material for a permanent coating film such as a solder resist has a problem that it is not always sufficient in terms of water resistance. This is because the alkali-developable resin composition is mainly composed of a resin having a hydrophilic group in order to impart alkali developability, and such a hydrophilic group is used for water, steam, chemicals, etc. on the cured product. This is thought to be because it may cause the penetration of the resin and reduce the adhesion between the resist film and copper.

It is known that in an alkali-developed resin composition, water resistance is improved by blending a photopolymerizable compound having a urethane bond or an isocyanurate ring as well as an ethylenically unsaturated bond to increase the crosslink density. (For example, Patent Document 1). However, since the obtained cured product is hard and brittle, the adhesion is lowered, and it is difficult to achieve both water resistance and adhesion.

Japanese Patent No. 5181223

Therefore, an object of the present invention is an alkali-developed resin composition capable of obtaining a cured product having excellent water resistance and adhesion, a dry film having a resin layer obtained from the composition, the composition or the dry film. It is an object of the present invention to provide a cured product of the resin layer of the above and a printed wiring board having the cured product.

As a result of diligent studies in view of the above, the present inventors have found that the above problems can be solved by using surface-treated barium sulfate and surface-treated talc, and have completed the present invention.

That is, the alkali-developable resin composition of the present invention comprises (A) a photosensitive prepolymer, (B) a photosensitive (meth) acrylate compound, (C) a photopolymerization initiator, and (D) a surface-treated barium sulfate. , (E) Surface-treated talc and (F) Thermosetting resin.

In the alkali-developable resin composition of the present invention, the surface treatment agent for barium sulfate (D) surface-treated contains a hydroxide of one or more metal elements selected from Al, Si and Zr. Is preferable.

In the alkali-developable resin composition of the present invention, it is preferable that the surface treatment agent for the surface-treated talc (E) contains a vinylsilane-based coupling agent.

In the alkali-developed resin composition of the present invention, the total content of (D) surface-treated barium sulfate and (E) surface-treated talc is 25 to 100% by mass of the total inorganic filler component. Is preferable.

The dry film of the present invention is characterized by having a resin layer obtained by applying the alkali-developable resin composition to the film and drying it.

The cured product of the present invention is characterized by being obtained by curing the resin composition capable of developing alkali or the resin layer of the dry film.

The printed wiring board of the present invention is characterized by having the cured product.

According to the present invention, an alkali-developed resin composition capable of obtaining a cured product having excellent water resistance and adhesion, a dry film having a resin layer obtained from the composition, the composition or the dry film. A cured product of the resin layer and a printed wiring board having the cured product can be provided.

The alkali-developed resin composition of the present invention comprises (A) a photosensitive prepolymer, (B) a photosensitive (meth) acrylate compound, (C) a photopolymerization initiator, and (D) a surface-treated barium sulfate. It is characterized by containing (E) a surface-treated talc and (F) a thermosetting resin. In the present invention, it is important that barium sulfate and talc are surface-treated, and by blending these two types of inorganic fillers, both water resistance and adhesion can be achieved.

In addition, in this specification, (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.

[(A) Photosensitive prepolymer]
As the photosensitive prepolymer (A), a photosensitive prepolymer having an ethylenically unsaturated double bond in the molecule can be preferably used. Further, it is more preferable that the (A) photosensitive prepolymer is a carboxyl group-containing photosensitive prepolymer. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

Specific examples of the carboxyl group-containing photosensitive prepolymer include compounds (either oligomers and polymers) as listed below.
(1) An unsaturated carboxylic acid such as (meth) acrylic acid, an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene, and a photosensitive monomer as described below. A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by copolymerization. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcoic compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds. A carboxyl group-containing urethane resin produced by a double addition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. During synthesis, a compound having one hydroxyl group and one or more (meth) acryloyl groups is added to a molecule such as hydroxyalkyl (meth) acrylate to form a terminal (meth) acrylic, and the carboxyl having an ethylenically unsaturated group. Group-containing polyurethane resin.
(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based During the synthesis of a terminal carboxyl group-containing urethane resin formed by reacting an acid anhydride with the end of the urethane resin by a double addition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. , A compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate, and terminal (meth) acrylicized, carboxyl group-containing polyurethane having an ethylenically unsaturated group. resin.
(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Meta) A carboxyl group-containing polyurethane resin having an ethylenically unsaturated group by a double addition reaction of an acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.
(5) During the synthesis of the resin of (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups is added to a molecule such as hydroxyalkyl (meth) acrylate to form terminal (meth) acrylic. A carboxyl group-containing polyurethane resin having an ethylenically unsaturated group.
(6) During the synthesis of the resin according to (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are added to the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate equimolar reaction product. A carboxyl group-containing polyurethane resin having an ethylenically unsaturated group, which has been subjected to terminal (meth) acrylicization by adding the compound having the compound.
(7) A (meth) acrylic acid is reacted with the above-mentioned polyfunctional epoxy resin, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to the hydroxyl group existing in the side chain. A carboxyl group-containing resin having an ethylenically unsaturated group. Here, the polyfunctional epoxy resin is preferably solid.
(8) A polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the generated hydroxyl group. A carboxyl group-containing resin having a saturated group. Here, the bifunctional epoxy resin is preferably solid.
(9) A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by reacting a bifunctional oxetane resin as described above with a dicarboxylic acid and adding a dibasic acid anhydride to the generated primary hydroxyl group.
(10) Reaction production obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by reacting a compound with a polybasic acid anhydride.
(11) Obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by reacting a reaction product with a polybasic acid anhydride.
(12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth). Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine with respect to the alcoholic hydroxyl group of the obtained reaction product. A carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by reacting a polybasic acid anhydride such as an acid.
(13) In addition to the resin according to any one of (1) to (12) above, one epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing resin having an ethylenically unsaturated group, to which a compound having a group is added.

Since the carboxyl group-containing photosensitive prepolymer having an ethylenically unsaturated group as described above has a large number of carboxyl groups in the side chain of the backbone polymer, it can be developed with an alkaline aqueous solution.

Among the specific examples of the above-mentioned carboxyl group-containing resin, the following resin (A1) can be used as the carboxyl group-containing resin having an ethylenically unsaturated group (12).
The above (a) includes an epoxy compound having two or more epoxy groups in one molecule, (b) a phenol compound having an alcoholic hydroxyl group-containing substituent, and (c) an unsaturated group-containing monocarboxylic acid. ) The phenolic hydroxyl group of the phenol compound having the above (b) alcoholic hydroxyl group-containing substituent is 0.2 to 0.6 equivalent with respect to 1 equivalent of the epoxy group of the epoxy compound, and (b) alcoholic hydroxyl group-containing substituent. The reaction product (X) obtained by reacting the phenolic hydroxyl group of the phenolic compound having a group with the carboxyl group of the (c) unsaturated group-containing monocarboxylic acid in a total ratio of 0.8 to 1.3 equivalents. A carboxyl group-containing resin having an ethylenically unsaturated group (A1) obtained by reacting the alcoholic hydroxyl group of (d) with an anhydrous group of (d) polybasic acid anhydride at a ratio of 99: 1 to 1:99.

（式中、ｘは０〜５までの整数で、ベンゼン環の水素と置換する置換基Ｒ^１の数を表わし、Ｒ^１はｘが１のとき、炭素数１〜４の飽和又は不飽和アルキル基、フェニル基又はシクロヘキシル基の中から選ばれる一つの置換基を表わし、ｘが２以上のとき、前記置換基の中からｘ個選ばれる同一又は異なる複数の置換基を表わす。ｙは１〜５の整数で、ベンゼン環の水素と置換する置換基Ｒ^２−ＯＨの数を表わし、Ｒ^２は、ｙが１のとき、炭素数１〜２０の直鎖、分岐又は環状のアルキル基または

（ここで、Ｒ^３はエチレン基、プロピレン基、ヒドロキシプロピレン基または

（ｎ＝２または３、Ｚ＝１または２）である。）の中から選ばれる一つの置換基を表わし、ｙが２以上のとき、前記置換基の中からｙ個選ばれる同一又は異なる複数基の置換基を表わす。） The phenol compound (b) having an alcoholic hydroxyl group-containing substituent is not particularly limited, but a compound represented by the following formula (1) is preferable. Particularly preferred is p-hydroxyphenethyl alcohol. As these phenol compounds (b) having an alcoholic hydroxyl group-containing substituent, one type can be used alone, or two or more types can be used in combination.

(Wherein, x is an integer from 0 to 5, represents the number of substituents R ^1, which replaces the hydrogen of the benzene ring, when R ¹ is x is 1, saturated or unsaturated alkyl of 1 to 4 carbon atoms It represents one substituent selected from a group, a phenyl group or a cyclohexyl group, and when x is 2 or more, it represents a plurality of the same or different substituents selected from x of the above substituents. An integer of 5 represents the number of substituent R ^2- OH that replaces hydrogen in the benzene ring, where R ² is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms when y is 1.

(Here, R ³ is an ethylene group, a propylene group, a hydroxypropylene group or

(N = 2 or 3, Z = 1 or 2). ), And when y is 2 or more, it represents the same or different multiple substituents selected from y of the substituents. )

The acid value of the (A) photosensitive prepolymer is preferably in the range of 30 to 200 mgKOH / g, more preferably in the range of 30 to 150 mgKOH / g, and particularly preferably in the range of 45 to 120 mgKOH / g. (A) When the acid value of the photosensitive prepolymer is 30 mgKOH / g or more, alkaline development is good, while when it is 200 mgKOH / g or less, dissolution of the exposed part by the developing solution can be suppressed, so that it is more than necessary. It is possible to satisfactorily draw a patterned resist by suppressing thinning of lines and, in some cases, dissolution and peeling with a developing solution regardless of whether the exposed portion and the unexposed portion are exposed.

Further, the weight average molecular weight Mw (polystyrene-equivalent weight average molecular weight) of the (A) photosensitive prepolymer as measured by, for example, gel permeation chromatography (GPC) differs depending on the resin skeleton. It is preferably greater than 000 and less than 150,000, more preferably in the range of 5,000 to 100,000. When the weight average molecular weight is larger than 4,000, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, film loss can be suppressed during development, and resolution deterioration can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good.

(A) As the photosensitive prepolymer, one type may be used alone, or two or more types may be used in combination. The blending amount of the photosensitive prepolymer (A) is preferably 10 to 70% by mass, more preferably 30 to 50% by mass, in terms of solid content, per alkali-developed resin composition.

[(B) Photosensitive (meth) acrylate compound]
As the (B) photosensitive (meth) acrylate compound, a known and commonly used (meth) acrylate-based oligomer or (meth) acrylate-based monomer that can be used as a photosensitive monomer can be used. (B) As the photosensitive (meth) acrylate compound, one type may be used alone, or two or more types may be used in combination.

Examples of the (meth) acrylate-based oligomer include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, and epoxy urethane (meth). ) Acrylic, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate and the like.

Examples of the (meth) acrylate-based monomer include (meth) acrylamides such as acrylamide, methacrylicamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylicamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylacrylamide. Kind: Allyl compounds such as triallyl isocyanurate, diallyl phthalate, diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfreel (meth) acrylate, isobolonyl (meth) acrylate, phenyl ( Esters of (meth) acrylic acids such as meta) acrylates and phenoxyethyl (meth) acrylates; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates and pentaerythritol tri (meth) acrylates. Classes: alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth). ) Acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other alkylene polyol poly (meth) acrylate; Polyoxyalkylene glycol poly (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimetylolpropan triacrylate, propoxylated trimethylol propantri (meth) acrylate; hydroxypivalic acid Poly (meth) acrylates such as neopentyl glycol ester di (meth) acrylate; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate can be mentioned.

The blending amount of the (B) photosensitive (meth) acrylate compound is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the (A) photosensitive prepolymer.

[(C) Photopolymerization Initiator]
As the photopolymerization initiator (C), any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used.

Examples of the photopolymerization initiator (C) include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis-. (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4) , 6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819 manufactured by BASF Japan) and other bisacylphosphine oxides; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2 , 4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan) Monoacylphosphine oxides such as IRGACURE TPO); 1-hydroxy-cyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one , 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-one Hydroxyacetophenones such as phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, Benzoyls such as p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-Propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1-[ 4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and other acetophenones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthons such as thioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylantraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, Anthraquinones such as 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate and p-dimethylbenzoic acid ethyl ester Classes; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-Il]-, Oxime esters such as 1- (O-acetyloxime); bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-) Pyrrole-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyll-1-yl) ethyl) phenyl] titanocene such as titanium; Examples thereof include phenyldisulfide 2-nitrofluorene, butyloin, anisoine ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like. (C) As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.

Among the photopolymerization initiators, it is preferable to use a photopolymerization initiator having excellent surface curability because a cured product having more excellent water resistance can be obtained. Further, the photopolymerization initiator having excellent surface curability preferably has an absorption wavelength of 250 to 450 nm, more preferably 250 to 400 nm. Examples of the photopolymerization initiator having excellent surface curability include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- (4-methylthiophenyl) -2-. Examples thereof include morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like.

The blending amount of the (C) photopolymerization initiator is preferably 1 to 25 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the (A) photosensitive prepolymer.

[(D) Surface-treated barium sulfate]
(D) The method for preparing the surface-treated barium sulfate is not particularly limited, but at least one selected from hydroxides and oxides of one or more metal elements selected from Al, Si and Zr as the surface treatment agent. Can be adjusted by subjecting one to barium sulfate. Specific examples of the surface treatment agent include hydrous silicic acid, hydrous non-crystalline silicon dioxide, aluminum hydroxide, zirconium oxide and the like. Examples of commercially available barium sulfate treated with such a surface treatment agent include B-30, B-31, B-32, B-33, B-34, B-35, and B-35T manufactured by Sakai Chemical Co., Ltd. Can be mentioned.

Moreover, you may use an organic silane compound as a surface treatment agent.

The average primary particle size of the surface-treated barium sulfate (D) is preferably 0.1 to 1 μm, more preferably 0.1 to 0.5 μm.

The amount of the surface-treated barium sulfate (D) is preferably 55 to 150 parts by mass, more preferably 60 to 100 parts by mass, based on 100 parts by mass of the (A) photosensitive prepolymer.

[(E) Surface-treated talc]
(E) The method for adjusting the surface-treated talc is not particularly limited, but the surface-treating agent includes silanes such as vinylsilane-based coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, and mercaptosilane-based coupling agents. It can be adjusted by using a system coupling agent, an organosilazane compound, a titanate system coupling agent, or the like. Examples of the vinylsilane-based coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxysilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxy. Propyltriethoxysilane is preferred. As the aminosilane-based coupling agent, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2- (aminoethyl) aminopropyltrimethoxysilane are preferable. .. Examples of the epoxysilane-based coupling agent include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, and (3,4-epoxycyclohexyl) ethyltri. Methoxysilane is preferred. As the mercaptosilane-based coupling agent, mercatopropyltrimethoxysilane and mercatopropyltriethoxysilane are preferable. Further, silane-based coupling agents such as methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, imidazolesilane, and triazinesilane can also be preferably used. As the organosilazane compound, hexamethyldisilazane, hexaphenyldisilazan, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane are preferable. Examples of the titanate-based coupling agent include butyl titanate dimer, titanium octylene glycolate, diisopropoxytitanium bis (triethanolamineate), dihydroxytitanium bislactate, dihydroxybis (ammonium lactate) titanium, and bis (dioctylpyrophosphate) ethylene titanate. Bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphate) titanate, tetraoctylbis (ditri) Decylphosphite) titanate, tet (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, isopropyltricylphenyl titanate, isopropyltriisostearoyl titanate, isopropylisostearoyldi Acrylic titanates, isopropyldimethacrylisostearoyl titanates, isopropyltri (dioctylphosphate) titanates, isopropyltridodecylbenzenesulfonyl titanates, isopropyltris (dioctylpyrophosphate) titanates, and isopropyltri (N-amideethyl / aminoethyl) titanates are preferred.

Among the surface treatment agents, silane-based coupling agents are preferable, vinylsilane-based coupling agents are more preferable, and methacrysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyl. More preferred are methacryloxysilane-based coupling agents such as methyldiethoxysilane and 3-methacryloxypropyltriethoxysilane.

(E) The surface-treated talc may be a commercially available talc that has been surface-treated. For example, talc obtained by surface-treating Microace K1 manufactured by Nippon Tarku Co., Ltd. with a vinylsilane coupling agent may be used. Good.

(E) The average primary particle size of the surface-treated talc is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm.

The amount of the surface-treated talc (E) is preferably 5 to 45 parts by mass with respect to 100 parts by mass of the (A) photosensitive prepolymer.

The ratio of the contents of (D) surface-treated barium sulfate and (E) surface-treated talc is, for example, 40 to 90: 10 to 60, and 55 to 90: 10 to 10 from the viewpoint of reducing the water absorption rate. It is preferably 45.

In addition, the alkali-developable resin composition of the present invention contains (D) surface-treated barium sulfate and (E) other inorganic fillers other than surface-treated talc as long as the effects of the present invention are not impaired. You may. Other inorganic fillers include, for example, silica, crystalline silica, Neuburg silica soil, aluminum hydroxide, glass powder, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium titanate, iron oxide. , Non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc flower and the like. These may or may not be surface treated. It may also contain unsurface-treated barium sulfate and talc.

The total content of the (D) surface-treated barium sulfate and (E) surface-treated talc is preferably 25 to 100% by mass, preferably 30 to 100% by mass of the total inorganic filler component. Is more preferable, and 50 to 100% by mass is further preferable.

The (D) surface-treated barium sulfate and (E) surface-treated talc may be blended in the surface-treated state in the alkali-developable resin composition of the present invention. The surface-untreated barium sulfate or talc and the surface-treating agent may be separately blended to perform the surface treatment in the composition, but the surface treatment is preferable in advance. By surface-treating in advance, it is possible to prevent deterioration of crack resistance and the like due to the surface-treating agent that may remain when the ingredients are mixed separately and are not consumed in the surface treatment.

[(F) Thermosetting resin]
The thermosetting resin (F) may be any resin that is cured by heating and exhibits electrical insulation, and examples thereof include epoxy compounds, oxetane compounds, melamine resins, and silicone resins. These may be used together.

As the epoxy compound, a known and commonly used compound having one or more epoxy groups can be used, and among them, a compound having two or more epoxy groups is preferable. For example, monoepoxy compounds such as monoepoxy compounds such as butyl glycidyl ether, phenylglycidyl ether, and glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, alicyclic epoxy resin, trimethylolpropan polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, Two or more epoxy groups in one molecule such as ethylene glycol or propylene glycol diglycidyl ether, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyltris (2-hydroxyethyl) isocyanurate, etc. Examples thereof include compounds having. These can be used alone or in combination of two or more, depending on the required characteristics.

Specific examples of the compound having two or more epoxy groups include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055 manufactured by DIC Corporation, and Nippon Steel & Sumikin Chemical Co., Ltd. Epoxy YD-011, YD-013, YD-127, YD-128, Dow Chemical Japan Co., Ltd. E. R. 317, D.I. E. R. 331, D. E. R. 661, D.I. E. R. 664, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei E-Materials Co., Ltd. E. R. 330, A. E. R. 331, A. E. R. 661, A. E. R. Bisphenol A type epoxy resin such as 664; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152 and Epicron 165 manufactured by DIC Corporation, Epototo YDB-400 and YDB-500 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and D.D. E. R. 542, Sumitomo Chemical's Sumi-Epoxy ESB-400, ESB-700, Asahi Kasei E-Materials' A.M. E. R. 711, A. E. R. Brominated epoxy resin such as 714; jER152, jER154 manufactured by Mitsubishi Chemical Corporation, D.D. E. N. 431, D.I. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., EPPN-201, EOCN-1025 manufactured by Nippon Kayaku Co., Ltd. EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical's Sumi-Epoxy ESCN-195X, ESCN-220, Asahi Kasei E-Materials' A.M. E. R. ECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. , Novolak type epoxy resin such as Epicron N-680, N-690, N-695 (all trade names) manufactured by DIC; Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd., Epototo manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Bisphenol F type epoxy resin such as YDF-170, YDF-175, YDF-2004; Hydrogenated bisphenol A type epoxy resin such as Epototo ST-2004, ST-2007, ST-3000 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; JER604 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YH-434 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; Glycidylamine type epoxy resin such as Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd.; Hydant-in type epoxy resin; Epoxy resin; YL-933 manufactured by Mitsubishi Chemical Co., Ltd., T.D. manufactured by Dow Chemical Japan Co., Ltd. E. N. , EPPN-501, EPPN-502 and the like trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Co., Ltd. YL-6056, YX-4000, YL-6121 and the like bixilenol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin such as EBPS-200 manufactured by Kayakusha, EPX-30 manufactured by ADEKA, EXA-1514 manufactured by DIC; Bisphenol A novolac type epoxy resin such as jER157S manufactured by Mitsubishi Chemical Co., Ltd .; Tetraphenylol ethane type epoxy resin such as jERYL-931; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries; diglycidyl phthalate resin such as Blemmer DGT manufactured by Nikko Co., Ltd .; ZX-1063 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin such as ESN-190, ESN-360, DIC HP-4032, EXA-4750, EXA-4700 manufactured by Nippon Steel & Sumitomo Metal Corporation; HP-7200 manufactured by DIC , HP-7200H and other epoxy resins having a dicyclopentadiene skeleton; glycidyl methacrylate copolymerized epoxy resins such as CP-50S and CP-50M manufactured by Nichiyu Co., Ltd .; and cyclohexyl maleimide and glycidyl methacrylate copolymerized epoxy resins; Examples thereof include, but are not limited to, CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Nippon Steel & Sumitomo Metal Corporation). Among these, bisphenol A type epoxy resin, heterocyclic epoxy resin or a mixture thereof is particularly preferable because it is excellent in discoloration resistance.
One of these epoxy resins may be used alone, or two or more of these epoxy resins may be used in combination.

（式中、Ｒ^１は、水素原子または炭素数１〜６のアルキル基を示す）により表されるオキセタン環を含有するオキセタン化合物の具体例としては、３−エチル−３−ヒドロキシメチルオキセタン（東亞合成社製ＯＸＴ−１０１）、３−エチル−３−（フェノキシメチル）オキセタン（東亞合成社製ＯＸＴ−２１１）、３−エチル−３−（２−エチルヘキシロキシメチル）オキセタン（東亞合成社製ＯＸＴ−２１２）、１，４−ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン（東亞合成社製ＯＸＴ−１２１）、ビス（３−エチル−３−オキセタニルメチル）エーテル（東亞合成社製ＯＸＴ−２２１）などが挙げられる。さらに、フェノールノボラックタイプのオキセタン化合物なども挙げられる。これらオキセタン化合物は、上記エポキシ化合物と併用してもよく、また、単独で使用してもよい。 Next, the oxetane compound will be described. The following general formula (II),

As a specific example of the oxetane compound containing an oxetane ring represented by (in the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), 3-ethyl-3-hydroxymethyloxetane (Toa) OXT-101) manufactured by Synthetic Co., Ltd., 3-Ethyl-3- (phenoxymethyl) oxetane (OXT-211 manufactured by Toa Synthetic Co., Ltd.), 3-Ethyl-3- (2-ethylhexyloxymethyl) oxetane (OXT manufactured by Toa Synthetic Co., Ltd.) -212), 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (OXT-121 manufactured by Toa Synthetic Co., Ltd.), bis (3-ethyl-3-oxetanylmethyl) ether (Toa Synthetic) OXT-221) manufactured by the company, and the like. Further, a phenol novolac type oxetane compound and the like can also be mentioned. These oxetane compounds may be used in combination with the above epoxy compounds, or may be used alone.

The blending amount of the thermosetting resin (F) is preferably 20 to 80 parts by mass, more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.

(Curing catalyst)
A curing catalyst can be contained in the alkali-developed resin composition of the present invention. Specific examples of the curing catalyst include tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, phosphonium ylides, and the like. Or two or more types can be used in combination.

Among them, in particular, imidazoles such as trade names 2E4MZ, C11Z, C17Z, 2PZ, AZINE compounds of imidazoles such as trade names 2MZ-A, 2E4MZ-A, and isocyanurates of imidazoles such as trade names 2MZ-OK and 2PZ-OK. , Trade name 2PHZ, 2P4MHZ and other imidazole hydroxymethyl compounds (trade names are all manufactured by Shikoku Kasei Kogyo Co., Ltd.), dicyandiamide and its derivatives, melamine and its derivatives, diaminomaleonitrile and its derivatives, diethylenetriamine, triethylenetetramine, tetraethylene. Amines such as pentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide, 1,8-diazabicyclo [5,4,0] undecene-7 (trade name: DBU, manufactured by San Apro), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (trade name ATU, manufactured by Ajinomoto Co., Ltd.), or triphenylphosphine, tricyclohexylphosphine, tributyl Preferable examples include organic phosphine compounds such as phosphine and methyldiphenylphosphine.

The blending amount of the curing catalyst is preferably 0.5 to 5 parts by mass, more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.

(Organic solvent)
The alkali-developable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition, adjusting the viscosity when applied to a substrate or a carrier film, and the like. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol and propylene glycol monomethyl ether. , Dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether and other glycol ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbi Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha are known. Conventional organic solvents can be used. One of these organic solvents may be used alone, or two or more of them may be used in combination.

(Other optional ingredients)
Further, the alkali-developed resin composition of the present invention may contain other additives known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, leveling agents, thickening agents. Agents, adhesion-imparting agents, thixo-imparting agents, colorants, photoinitiator aids, sensitizers, thermoplastic resins, organic fillers, mold release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers , Stabilizers, phosphors and the like.

The alkali-developed resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.

Next, the dry film of the present invention has a resin layer obtained by applying and drying the alkali-developed resin composition of the present invention on a carrier film. When forming a dry film, first, the alkali-developed resin composition of the present invention is diluted with the above organic solvent to adjust the viscosity to an appropriate level, and then a comma coater, a blade coater, a lip coater, a rod coater, etc. Apply to a uniform thickness on the carrier film with a squeeze coater, reverse coater, transfer coater, gravure coater, spray coater, or the like. Then, the applied composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but is generally selected as appropriate in the range of 10 to 150 μm, preferably 15 to 60 μm after drying.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film and the like can be used. The thickness of the carrier film is not particularly limited, but is generally selected as appropriate in the range of 10 to 150 μm.

After forming a resin layer made of the alkali-developed resin composition of the present invention on a carrier film, a peelable cover is further applied to the surface of the film for the purpose of preventing dust from adhering to the surface of the film. It is preferable to laminate the films. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used. The cover film may be smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

In the present invention, the resin composition of the present invention may be applied on the cover film and dried to form a resin layer, and a carrier film may be laminated on the surface thereof. .. That is, either a carrier film or a cover film may be used as the film to which the alkali-developed resin composition of the present invention is applied when the dry film is produced in the present invention.

Further, the alkali-developed resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the above-mentioned organic solvent, and a dip coating method, a flow coating method, a roll coating method, etc. A tack-free resin is obtained by volatilizing and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. after applying by a method such as a bar coater method, a screen printing method, or a curtain coating method. Layers can be formed. Further, in the case of a dry film in which the above composition is applied onto a carrier film or a cover film, dried and wound as a film, the layer of the composition of the present invention is brought into contact with the base material by a laminator or the like on the base material. A resin layer can be formed by peeling off the carrier film after the film is attached to the film.

The base material includes a printed wiring board and a flexible printed wiring board whose circuit is formed of copper or the like in advance, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, and glass cloth / paper epoxy. , Synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc. are used for high frequency circuit copper-clad laminates, etc., and all grades (FR-4, etc.) of copper-clad laminates are used. Plates, other metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

The volatile drying performed after applying the alkali-developed resin composition of the present invention is performed by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. (using a steam-based air heating type heat source). It can be carried out by using a method of bringing hot air in the machine into countercurrent contact and a method of blowing the hot air from a nozzle onto a support).

The exposed portion (light-irradiated portion) is cured by applying the alkali-developable resin composition of the present invention, volatilizing and drying the solvent, and then exposing (light-irradiating) the obtained resin layer. .. Specifically, a contact type or a non-contact type is used to selectively expose with active energy rays through a photomask in which a pattern is formed, or to directly expose a pattern with a laser direct exposure machine. A resist pattern can be formed by developing the unexposed portion with a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution).

The exposure machine used for the above-mentioned active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. Further, a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser based on CAD data from a computer) can also be used. The lamp light source or the laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm. The amount of exposure for image formation varies depending on the film thickness and the like, but can be generally in the range of ^{20 to} 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developing solution includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. Alkaline aqueous solutions such as ammonia and amines can be used.

The alkali-developable resin composition of the present invention can be preferably used for forming a permanent protective film for a printed wiring board, and more preferably for forming a solder resist layer, an interlayer insulating layer, and a coverlay for a flexible printed wiring board. Can be done.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, "part" and "%" are all based on mass unless otherwise specified.

(Synthesis of photosensitive prepolymer)
Put 220 parts (1 equivalent) of cresol novolac type epoxy resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 220) into a four-necked flask equipped with a stirrer and a reflux condenser, add 218 parts of carbitol acetate, and add. It was melted by heating. Next, 0.46 parts of methyl hydroquinone was added as a polymerization inhibitor and 1.38 parts of triphenylphosphine was added as a reaction catalyst. The mixture was heated to 95-105 ° C., 50.4 parts (0.7 equivalents) of acrylic acid and 41.5 (0.3 equivalents) of p-hydroxyphenethyl alcohol were gradually added dropwise, and the mixture was reacted for 16 hours. This reaction product (hydroxyl group: 1.3 equivalents) was cooled to 80 to 90 ° C., 91.2 parts (0.6 equivalents) of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled, and then taken out. .. The carboxyl group-containing photosensitive resin thus obtained had a non-volatile content of 65% and a solid acid value of 83 mgKOH / g. Hereinafter, this reaction solution is referred to as a photosensitive prepolymer solution A-1.

(Examples 1 to 4, Comparative Examples 1 to 3)
According to the formulation shown in the table below, each component was blended, premixed with a stirrer, dispersed with a three-roll mill, and kneaded to prepare a main agent and a curing agent. The blending amount in the table indicates a mass part.

Ａ−１：上記で得た感光性プレポリマー溶液Ａ−１（上記（Ａ１）エチレン性不飽和基を有するカルボキシル基含有樹脂）
Ｂ−１：感光性（メタ）アクリレート化合物（ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート、日本化薬社製））
Ｃ−１：光重合開始剤（２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ＢＡＳＦジャパン社製）
Ｄ−１：堺化学社製Ｂ−３０
Ｅ−１：日本タルク社製ミクロエースＫ１をビニルシラン系カップリング剤で表面処理したタルク
Ｆ−１：熱硬化性樹脂（日本化薬社製ＲＥ−３０６（フェノールノボラックエポキシ樹脂）
Ｆ−２：熱硬化性樹脂（ダイセル社製エポリードＰＢ３６００、エポキシ化ポリブタジエン）
Ｆ−３：熱硬化性樹脂（三菱化学社製ＹＸ−４０００（ビフェニル型エポキシ樹脂）
＊１：ジシアンジアミド
＊２：ファーストゲンブルー５３８０
＊３：クロモフタルエローＡＧＲ
＊４：消泡剤、信越化学工業社製
＊５：ポリヒドロキシカルボン酸エステル系添加剤、ビックケミー・ジャパン社製
＊６：メラミン
＊７：有機溶剤（ジプロピレングリコールモノメチルエーテル、ダウケミカル社製）
＊８：出光興産社製「イプゾール」＃１５０
＊９：日本タルク社製ミクロエースＫ−１
＊１０：堺化学工業社製硫酸バリウム１１０
＊１１：シリカ、東ソー・シリカ社製
＊１２：大日精化工業社製ダイミックビーズ ＵＣＮ−５０５０Ｄクリヤー

A-1: The photosensitive prepolymer solution A-1 obtained above (the above (A1) carboxyl group-containing resin having an ethylenically unsaturated group).
B-1: Photosensitive (meth) acrylate compound (DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.))
C-1: Photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, manufactured by BASF Japan Ltd.)
D-1: Sakai Chemical Co., Ltd. B-30
E-1: Talc F-1 made by surface-treating Microace K1 manufactured by Nippon Kayaku Co., Ltd. with a vinylsilane coupling agent: Thermosetting resin (RE-306 (phenol novolac epoxy resin) manufactured by Nippon Kayaku Co., Ltd.)
F-2: Thermosetting resin (Epolide PB3600 manufactured by Daicel, epoxidized polybutadiene)
F-3: Thermosetting resin (YX-4000 (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation)
* 1: Diocyandiamide * 2: Firstgen Blue 5380
* 3: Chromophthalero AGR
* 4: Defoamer, manufactured by Shin-Etsu Chemical Industry Co., Ltd. * 5: Polyhydroxycarboxylic acid ester-based additive, manufactured by Big Chemie Japan Co., Ltd. * 6: Melamine * 7: Organic solvent (dipropylene glycol monomethyl ether, manufactured by Dow Chemical Co., Ltd.)
* 8: Idemitsu Kosan "Ipsol"# 150
* 9: Micro Ace K-1 manufactured by Japan Talc
* 10: Barium sulfate 110 manufactured by Sakai Chemical Industry Co., Ltd.
* 11: Silica, manufactured by Toso Silica * 12: Dimic beads manufactured by Dainichiseika Kogyo Co., Ltd. UCN-5050D Clear

The obtained main agent and the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 obtained by mixing the main agent and the curing agent were evaluated according to the following. The results are shown in the table below.

(Viscosity / TI)
0.2 ml of the main agent obtained above and the resin compositions of each Example and Comparative Example were collected, and used with a cone plate type viscometer (TV-33H manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and a rotation speed of 5 rpm (shear). The viscosity of the 30-second value at a speed of 10 ^-1 s) and the viscosity of the 30-second value at a rotation speed of 50 rpm (shear velocity of 100 ^-1 s) were measured. The viscosities in Table 2 are viscosity values at a shear rate of 10 ^-1 s.
TI = [Viscosity value at shear rate 10 ^-1 s] / [Viscosity value at shear rate 100 ^-1 s]

(sensitivity)
The resin compositions of each Example and Comparative Example were applied to the entire surface of a washed copper solid substrate after drying by screen printing to a size of 10 μm, and dried at 80 ° C. for 10 minutes in a hot air circulation type drying oven. A step tablet (Kodak No. 2) is applied onto this coating film, exposed with an exposure machine equipped with a metal halide lamp manufactured by ORC Manufacturing Co., Ltd. at an exposure amount of 500 to 700 mJ / cm ² , and with a 1 wt% Na ₂ CO ₃ aqueous solution. The number of remaining stages after development at 30 ° C. for 1 minute at a spray pressure of 0.2 MPa was examined. The larger the number of remaining stages, the better the sensitivity, which is preferable.

(Drying control width)
The resin compositions of each Example and Comparative Example were screen-printed on the patterned copper foil substrate so as to have a thickness of 20 μm after drying. Four substrates on which the resin composition was applied were prepared for each Example and Comparative Example, and dried at 80 ° C. From the start of drying to 60 to 90 minutes, one substrate was taken out for each Example and Comparative Example every 10 minutes, and each substrate was cooled to room temperature.
Each substrate having a different drying time was developed with a 1 wt% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.2 MPa at 30 ° C. for 1 minute, and under each drying condition, the copper was visually observed after development to evaluate the developability. As a result, it was tested whether the components of the resin composition remained as a residue. The width of the developable drying temperature and the drying time is called the drying control width, and the longer the developable drying time, the wider the margin due to drying, and the easier it is to control the production by the substrate manufacturing process.
◯: No residue on the substrate.
Δ: There is a residue on a part of the substrate.
X: There is a residue on the entire surface of the substrate.

(Preparation of evaluation substrate for evaluation of cured product characteristics)
The resin compositions of each Example and Comparative Example were applied over the entire surface of the patterned copper foil substrate so that the dry film thickness was 20 μm, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using an exposure apparatus equipped with a high-pressure mercury lamp on this substrate, pattern exposure was performed with the optimum exposure amount determined as described below, and then development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.2 MPa at 30 ° C. for 1 minute. And got a pattern. The substrate was heat-cured at 150 ° C. for 60 minutes and then allowed to cool to room temperature. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated light intensity of 1000 mJ / cm ² , to obtain an evaluation substrate for evaluating the characteristics of the cured product in which the cured product pattern was formed.

(Optimal exposure)
The resin compositions of each Example and Comparative Example were applied to the entire surface of a circuit pattern substrate having a copper thickness of 35 μm, which had been bafflor-polished, washed with water, and dried by a screen printing method, and in a hot air circulation type drying oven at 80 ° C. It was dried for 30 minutes.
After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure device equipped with a metal halide lamp manufactured by ORC Manufacturing Co., Ltd., and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.2 MPa at 30 ° C. for 1 minute. The optimum exposure amount was set when the pattern of the step tablet remaining after the above was 6 steps.

(Pencil hardness)
The cured coating film of the evaluation substrate for evaluating the characteristics of the cured product was tested according to the test method of JIS C 5400, and the highest hardness without damaging the coating film was observed.

(Adhesion)
The evaluation substrate for evaluating the characteristics of the cured product was cross-cut in a grid pattern according to the test method of JIS D 0202, and a peel test was performed to evaluate the peeling of the resist layer.

(Solder heat resistance)
A rosin-based flux was applied to the evaluation substrate for evaluating the characteristics of the cured product, and then immersed in a solder bath previously set at 260 ° C. Then, after washing the flux with the modified alcohol, the swelling and peeling of the resist layer were visually evaluated. The evaluation criteria are as follows.
◯: No peeling was observed even after repeating the immersion for 10 seconds three times.
Δ: A little peeling occurs when the immersion is repeated 3 times for 10 seconds.
X: The resist layer swells and peels off within 3 times of immersion for 10 seconds.

(Solvent resistance)
The evaluation substrate for evaluating the characteristics of the cured product was immersed in propylene glycol monomethyl ether acetate at room temperature for 30 minutes, and soaking and leaching of the coating film were visually confirmed, and further, peeling due to tape peeling was confirmed. The judgment criteria are as follows.
◯: No change is observed in the coating film.
Δ: The coating film has changed slightly.
X: The coating film has swelling or swelling and falling off.

(Water absorption rate)
A cured product pattern of the resin composition was formed on the glass substrate whose weight was measured in advance in the same manner as in the production of the evaluation substrate for evaluating the characteristics of the cured product, and the total weight was measured. Then, after immersing in ion-exchanged water at 25 ° C. for 24 hours, the weight was measured, and the rate of increase in weight was defined as the water absorption rate and evaluated according to the following criteria.
◯: Water absorption rate is 1.0% or more and less than 1.5%.
Δ: Water absorption rate is 1.5% or more and less than 2.0%.
X: Water absorption rate 2.0% or more.

(Insulation resistance)
On the FR-4 substrate on which the IPC-B-25A comb-shaped electrode described in IPC-SM-840-D is formed, a cured product of the resin composition is prepared in the same manner as in the production of the evaluation substrate for evaluating the characteristics of the cured product. A pattern was formed to prepare an evaluation substrate for measuring insulation resistance. The insulation resistance value of the obtained evaluation substrate was measured under the following conditions and used as the initial value. After that, IPC-SM-840-D Class H (cycle of 25 to 65 ° C ± 2 ° C, humidity 90% + 3%, -5%, VDC = 50V, measured 100V, T = 160h, D coupon, 500 megaΩ The insulation resistance value processed according to the above) was measured under the following conditions.
Insulation resistance measurement conditions:
DC100V was applied to the evaluation substrate, and the insulation resistance value was measured. The insulation resistance value after the treatment was evaluated according to the following criteria.
◯: Insulation resistance is 1.0 × 10 ¹² Ω or more.
×: Insulation resistance is less than 1.0 × 10 ¹² Ω.

(Dielectric constant / dielectric loss tangent after humidification)
The cured coating film of the evaluation substrate for evaluating the characteristics of the cured product was treated under the humidifying conditions of 25 ° C. to 65 ° C. (cycle), 90% RH, and 7 days treatment, and then MULTI-FREQUENCY LCR manufactured by Hewlett-Packard Japan. The permittivity and dielectric loss tangent were measured by the resonance method using METER 4275A. The dielectric constant and dielectric loss tangent were measured according to JIS K 6911. The permittivity and the dielectric loss tangent were evaluated according to the following criteria.
[Dielectric constant after humidification (Df)]
◯: Less than 5.0.
×: 5.0 or more.
[Dissipation factor (Dk) after humidification]
◯: Less than 0.4.
X: 0.4 or more.

(Solder heat resistance after moisture absorption)
The evaluation substrate for evaluating the characteristics of the cured product was humidified under the conditions of PCT (121 ° C., 100% RH, 24 hours), and then a water-soluble flux (W-2704, manufactured by MEC) was applied to the substrate. The substrate was immersed in a solder bath at 288 ° C. for 15 seconds. Next, the substrate was put into water at about 60 ° C. and left for 10 minutes (flux removing step), and then the substrate was taken out of the water and the moisture on the surface of the substrate was thoroughly wiped off. Then, in this substrate, the presence or absence of swelling or peeling of the resist layer was evaluated. The judgment criteria are as follows.
◯: No swelling or peeling.
Δ: There is slight swelling or slight peeling.
X: There is swelling or peeling.

It can be seen that the alkali-developed resin compositions of Examples 1 to 4 are excellent in water resistance because they have excellent adhesion, low water absorption, and high insulation resistance after IPC cycle treatment. Comparative Example 1 in which (D) surface-treated barium was replaced with surface-untreated barium, (E) Comparative Example 2 in which surface-treated talc was replaced with surface-treated talc, and It can be seen that the alkali-developed resin composition of Comparative Example 3 in which both barium sulfate and talc are surface-untreated is inferior in water resistance because it has a high water absorption rate and low insulation resistance after the IPC cycle treatment.

In addition, the alkali-developed resin compositions of Examples 1 to 4 were also excellent in dielectric constant after humidification, dielectric loss tangent, and solder heat resistance after moisture absorption.

Claims (6)

(A) Photosensitive prepolymer, (B) Photosensitive (meth) acrylate compound, (C) Photopolymerization initiator, (D) Surface-treated barium sulfate, (E) Surface-treated talc, and (F) ) A resin composition containing a thermosetting resin .
As the (C) photopolymerization initiator, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopro Contains any of pan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
The surface treatment agent for barium sulfate (D) surface-treated contains a hydroxide of one or more metal elements selected from Al, Si and Zr.
(E) An alkali-developable resin composition, wherein the surface-treated talc surface-treating agent contains a vinylsilane-based coupling agent . Wherein (D) the sum of the surface-treated barium sulfate (E) surface-treated talc content, alkali claim 1 Symbol mounting, characterized in that 25 to 100% by weight of the total inorganic filler component Developable resin composition. A dry film having a resin layer obtained by applying the alkali-developable resin composition according to claim 1 or 2 to a film and drying the film. A cured product obtained by curing the alkali-developable resin composition according to claim 1 or 2 . A cured product obtained by curing the resin layer of the dry film according to claim 3 . A printed wiring board comprising the cured product according to claim 4 or 5 .